Composition of matter comprising gelatin and polyvinyl urea or derivatives



Patented Apr. 19, 1949' COMPOSITION or MATTER COMPRISING onmm ANDPOLYVINYL mum on or:-

' arvArIvEs D. Jones, Easton, Pa., assignor toGeneral Aniline & FilmCorporation, New York, N. Y., a

corporation or Delaware No Drawing. Application October 23,1945,

' Serial No. 624,092

v 6Claims. (Cl. 260-8) 1; 2 The present inventionrelates to derivativesof Example 1 polyvinylisocyanate and moreparticularly to reactionproducts of polyvinylisocyanate with nitrogen-containing compounds.having at least one hydrogen on the nitrogen atom, as for example,ammonia and amines.

The new reaction products are compatible with gelatin and maybe used assubstitutes therefor, or in combination'tlierwith to produce newcompositions which arehighly useful in the photographic arts.

It is among the objects of my invention ,to produce new reactionproducts of polyvinylisocyanate. Y

It is a further object of my invention to produce new compositionscomprising gelatin and reaction products of polyvinylisocyanate' withnitrogen compounds having at least one hydrogen on the nitrogen.

According to my invention, the new reaction products are in generalprepared by reacting polyvinylisocyanate with a nitrogen compound havingat least one hydrogen on the nitrogen. as for example, ammonia andamines. Any amine having at least one hydrogen on the hi trogen may beutilized to react with the polyvinylisocyanate. There can be employedmonoand disubstituted amines. The amino nitrogen substituents may bealkyl, aryl; aralkyl, cycloparaflln, or an hydroxyalkyl group, or theamino nitrogen may be a member of a ring which may be heterocyclic. Asspecificexamples of suitable amines, there may be mentioned methylamine,ethylamine, propylamine, isopropylamine, butylamine, isobutylamine,dimethylarhine, die'thylamine, dipropylamine, aniline, diphenylamine,ethanolamine, diethanolamine, propanolamine,

cyclohexylamine, N-methyl-N-cyclohexylamine,

benzylamine, morpholine and 'pipe'ridine.

In the reaction involving the use of the amines,

the polyvinylisocyanate can be reacted at reflux temperature, and whenthe reaction is complete the converted polymer can be recovered byprecipitation in a diluent in which it isinsoluble, asfor example, ethylether.'

In the reaction oi? the po'lyvinylisocyanatewith ammonia it-i'spreferred to carry out the reaction at roomtemperature. Upon completionof the reaction, the converted polyvinylisocyanate can be recovered byprecipitating in a liquid in which the polymer is insoluble, as forexample, meth- To parts of morpholine were added 25 parts ofpolyvinylisocyanate and the solution was refluxed for 48 hours. Thepolymerwhich formed was precipitated as a hygroscopic tan powder bypouring the dark solution of the polymer into absolute ether. A yield of24 parts of the converted polymer was obtained. water-soluble, had asoftening point of about C. and a K value in Water of 54. Analysis.Calculated for (C'zHnOzNzn: N, 17.92. Found: 13.30.

Example-2 A mixture of 25 parts of polyvinylisocyanate and 102 parts ofethanolamine was refluxed for There was a slight evolution of heat' 48hours. when the reagents were mixed together. The solution obtained onrefluxing was distilled under aspirator pressure and the dark gummyresidue reprecipitated by dissolving in 320 parts .of absolute alcoholand pouring the resulting solution into 1500 parts of absolute ether.The precipitated product which was recovered tended to become gummy. Itwas water-soluble,-had a K value in water of 51 and was compatible withgelatin. Analysis: Calculated for (C5H10O2N2) a: N, 21.5. Found: N,20.77.

Example 3 A mixture of 1 0mm of polyvinylisocyana'te and 200 parts of28% aqueous ammonia solution were permitted to stand at room temperaturefor 12 hours. A dark solution'formed which was filtered and the filtratewas poured into an ex cess of methanol. There was isolated by.filtration a brown, hygroscopic powder which, on drying in a vacuumdesiccator, gave a yield-of 38 parts of the converted polymer. 7

That part of the polyvinylisocyanatewhich did not dissolve :in theconcentrated ammonia was treated with an-additional 100 parts ofammoniaand agitated for another 12 hours. Alloi' the polyvinylisocyanatedissolved in the ammonia and, on pouring the solution into methanol, the

converted polyvinylisocyanate precipitated and' i was filtered. ondrying, a yield of 20 parts of the converted polymer was obtained. cropsof. the converted polymer were water-soluble powders which gave slightlyviscous solu-' tionsand were compatible with gelatin. Analysisz-Calculated for (CaHsONzM: N, 31.4 Found:

compositions which may be obtained from the.

It was Both amps:

3 new derivatives of polyvinylisocyanate when employed in combinationwith gelatin.

Example 4 A solution was prepared from 0.5 part of thepolyvinylisocyanate-ethanolamine reaction product obtained according toExample 2, 0.5 part of gelatin and 9 parts of water. Films cast fromthis solution were clear, thereby indicating a good compatibility'of thepolyvinylisocyanate reaction product with gelatin.

Example 6 A solution was prepared containing 0.5 part of gelatin, 0.5part oi the polyvinylisocyanateammonia reaction product obtainedaccording to Example 3, and 9 parts oi water. When the solution wascast, a clear film was obtained.

Instead of the ethanolamine and morpholine oi Examples 2 and 3, it is tobe understood that the polyvinylisocyanate may be reacted in a similarmanner with other amines, such as those mentioned hereinabove. Theproportions oi! the reagents may be varied. Thus, thenitrogen-containing compounds may be employed in from less than to anexcess of the base molecular equivalent of the polyvinylisocyanate.Thus, from about 0.75 to about mols of the nitrogen compound may beemployed for each base mol of polyvinylisocyanate. However, it ispreferred to use the nitrogen compound in excess.

The temperature of the reaction may be varied depending on thevolatility oi the nitrogen-containing compounds. The reaction may becarried out at room temperature or at temperatures above or below roomtemperature. Where the nitrogen-containing compounds are volatile, thereaction may be carried out at elevated temperatures under pressure in asealed reaction vessel. In the case of the amines, reflux temperatureshave been found to be satisfactory for carrying out the conversion ofthe polyvinylisocyanate. In general, the reaction time may vary fromapproximately 12 hours to 48 hours. With higher temperatures the time oftreatment may be shortened, whereas when operating at low temperaturesthe time required is increased.

The polyvinylisocyanate employed as a starting material may be obtainedby introducing acrylyl chloride into a suspension of sodium azide indimethyliormamide, permitting the reaction to proceed at about 90 C. fora length of time sufilcient to form a suspension oi polyvinylisocyanatein the dimethylformamide, and then precipitating the polymer by dilutingthis suspension with ether. The polymer is finally recovered byfiltration. The process of producing polyvinylisocyanate comprises thesubject matter of my copending application, Serial No. 624,- 093, filedOctober 23, 1945.

The products obtained by the reaction of polyvinylisocyanate and thenitrogen-containing compounds are believed to be polyvinylureas 4whichcorrespondtotheprobablegeneraliorwherein R and R'may be hydrogen,alkyl, aryl, aralkyl, cycloparaifin. or hydroxyalkyl groups; or R and Rtaken together with the N may form a ring which may be heterocyclic.Thus, for example, R and It may be methyl, ethyl, propyl, isopropyl,butyl, isobutyl, phenyl. hydroxyprowl. cyclohexyl, benzyl; or when takentogether with the N, morpholine or piperidine. B. and B. may be the sameor different Thus, the reaction products of Examples 1, 2 and 3 may berepresented by the following probable formulas:

E'xample 1 r'CHr-CH 1 Example 2 ['CHr-CH 1 (Polyvinylethanolurea)Example 3 em-( m l aol I'm, (Poly inylurea) When the amines are utilizedin the reaction, substituted polyvinylureas are obtained. Thesubstituent on the N atom not directly attached to the vinyl group willdepend on the amine employed in the reaction. when ammonia is employedunsubstituted polyvinylurea is obtained.

I claim:

1. A composition of matter comprising gelatin and a polyvinyl urea,produced by reacting polyvinylisocyanate with a nitrogen compound 11-ing at least one reactive hydrogen atom attached to the nitrogen, of theclass consisting of ammonla, primary and secondary alkyl-, aryl-,aralkyl-, cycloparafllnicand hydroxyalkyl-amines, and heterocyclicnitrogen bases.

2. A composition as defined in claim 1, comprising substantially equalparts of gelatin and oi said polyvinyl urea.

3. A composition as defined in claim 1, wherein the amount of saidpolyvinyl urea exceeds 5o% 01 the amount of gelatin.

E I 9m 4. A ooinpositionpt matter comprising germs I UNITED STATESPATENTS and polyvinylmorpholineurea. s 1 5. Acomposition oi mattercomprising gelatin iss: p z fi and p01: nethanomrea" 2,191,654 I-Iaon 271940 6. A composition of matter comprising gelatin- 5 2 273 891 Pollacku Feb. 24 1942 and polyvinylursm I JONES- I 2,3 6,287 Cofiman Aug. 10,.1943 I v 2,334,476 Cofiman Nov. 16, 1943 REFERENCES CITED OTHERREFERENCES The following references are of record in the 10 Jones etal., Journal of organlc Chemistry, file of this patent: I 1 Nov. 1944,pp. 500,509.

